CN110205748A - A kind of composite nano-fiber membrane and the preparation method and application thereof of β-FeOOH/ polyacrylonitrile - Google Patents
A kind of composite nano-fiber membrane and the preparation method and application thereof of β-FeOOH/ polyacrylonitrile Download PDFInfo
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- CN110205748A CN110205748A CN201910362641.4A CN201910362641A CN110205748A CN 110205748 A CN110205748 A CN 110205748A CN 201910362641 A CN201910362641 A CN 201910362641A CN 110205748 A CN110205748 A CN 110205748A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/43—Acrylonitrile series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The present invention provides a kind of composite nano-fiber membrane and the preparation method and application thereof of β-FeOOH/ polyacrylonitrile, belongs to field of material technology.A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, comprising the following steps: polyacrylonitrile nanofiber film the preparation of polyacrylonitrile nanofiber film: is prepared using electrostatic spinning；Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing；Biomineralization processing: by the proportional arrangement of liquor ferri trichloridi and hydrochloric acid 2:1 by volume at mixed solution, stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 1-3min, then 10-14h is reacted under conditions of 55-65 DEG C, is then cleaned, is dried the composite nano-fiber membrane that β-FeOOH/ polyacrylonitrile is made.With preferable stability, mechanical performance, while there is super hydrophilic-underwater superoleophobic property, adsorption efficiency is high, can be recycled.
Description
Technical field
The invention belongs to field of material technology, specifically, the composite Nano for being related to a kind of β-FeOOH/ polyacrylonitrile is fine
Tie up film and the preparation method and application thereof.
Background technique
Electrostatic spinning technique is a kind of universal method for preparing fibre diameter from micron to nano-scale.Electrostatic spinning it is general
Thought can trace back to 1745, and after decades of development, electrospinning fibre has potential application, such as mistake in multiple fields
Filter, protective textile, drug conveying, organizational project, electronics and photonic device, sensor and catalysis；Wherein in sewage treatment side
Face, nearest research are dedicated to preparing nanofiber adsorbed film and filter membrane by the method for electrospinning；It is formed with nanofiber
Membrane material has high specific surface area, the nanoscale pore structure of internal height connection, and has adjustable pore structure
The characteristics of etc.；For traditional material for water treatment, these features greatly improve it in water-oil separating, dyestuff, weight
The separative efficiency of the removal process of metal reduces the energy consumption in separation process, also avoids secondary environmental pollution, at
For a kind of emerging sewage treating material；The high molecular polymer that can be used for electrostatic spinning common at present is polyacrylonitrile,
Kynoar, polyvinyl alcohol etc..
Usually have the characteristics that most of polymer film is similar using the polyacrylonitrile film that polyacrylonitrile goes out as raw material spinning, such as
Price is relatively cheap, excellent mechanical performance.But due to the natural property of polymer, polyacrylonitrile fibre membrane is anti-for organic matter
Pollution capacity is poor, and more difficult cleans to it after polluting；In addition the water pollution usually discharge of crude oil leakage and industry,
Itself is a complicated system, including soluble dye, heavy metal, insoluble organic matters for the waste water that seperation film faces；
And the environment that seperation film faces is also likely to be acid, alkali, the harsh complex environment of salt and organic reagent；Existing polyacrylonitrile is received
Rice tunica fibrosa is usually used in water-oil separating, the removal of dyestuff and heavy metal, but the contamination resistance of polyacrylonitrile nanofiber film,
Self-cleaning ability etc. is poor, while having poor stability in organic solvent.
Summary of the invention
The purpose of the present invention is to provide a kind of composite nano-fiber membranes of β-FeOOH/ polyacrylonitrile, have preferable steady
Qualitative energy, mechanical performance, while there is super hydrophilic-underwater superoleophobic property, adsorption efficiency is high, can be recycled conducive to industry
Change large-scale production.
Another object of the present invention is to provide a kind of preparation sides of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile
Method, method is simple, at low cost, the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile obtained have excellent stability can and
Absorption property.
Another object of the present invention is to provide a kind of composite nano-fiber membranes of β-FeOOH/ polyacrylonitrile at sewage
Application in reason, high treating effect can be repeated several times use.
In order to achieve the above object, the solution that the present invention uses is:
The present invention proposes a kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, including following step
It is rapid:
The preparation of polyacrylonitrile nanofiber film: polyacrylonitrile powder is uniformly mixed with N,N-dimethylformamide solution
Spinning solution is made, polyacrylonitrile nanofiber film, the polyacrylonitrile powder and N are then spun by electrostatic spinning apparatus,
The ratio of dinethylformamide solution is 1-1.4g:10mL；
Stabilization processes: the polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, in 235-240 DEG C of condition
Lower heat preservation 0.5-2h, keeps the temperature 0.4-0.6h under conditions of 245-250 DEG C, 0.5-2h is kept the temperature under conditions of 258-262 DEG C, so
It takes out to be cooled to room temperature afterwards and stabilized polyacrylonitrile nanofiber film is made；
Biomineralization processing:, will be steady by the proportional arrangement of liquor ferri trichloridi and hydrochloric acid 2:1 by volume at mixed solution
Surely the polyacrylonitrile nanofiber film changed, which is placed in the mixed solution, stirs 1-3min, then anti-under conditions of 55-65 DEG C
10-14h is answered, the composite nano-fiber membrane of obtained β-FeOOH/ polyacrylonitrile is then cleaned, dried.
The present invention proposes a kind of composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, is made by above-mentioned preparation method.
The present invention proposes a kind of application of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile in sewage treatment.
The composite nano-fiber membrane of a kind of β-FeOOH/ polyacrylonitrile provided by the invention and the preparation method and application thereof
Beneficial effect is to prepare polyacrylonitrile nanofiber film as substrate using electrostatic spinning first, the nano fibrous membrane of preparation has
High specific surface area is conducive to absorption；Then the stabilization processes for carrying out gradient increased temperature make polyacrylonitrile that cyclisation successively occur anti-
Answer, oxidation reaction and dehydrogenation reaction, polyacrylonitrile molecule structure are transformed into trapezium structure molecule, this aspect makes polyacrylonitrile
Nano fibrous membrane is in the state of one " not melting non-ignitable ", so that polymer film can be steady in common highly polar organic solvent
It is fixed to exist, while polyacrylonitrile nanofiber film strips have self-supporting property, this relative to traditional polyacrylonitrile nanofiber film,
The operability matter of polyacrylonitrile nanofiber film is improved, industrialization large-scale production is conducive to；On the other hand, introduce oxygen,
Nitrogen functional group improves the hydrophily of polyacrylonitrile nanofiber film；Biomineralization processing is finally carried out to draw in the process
β-FeOOH the nano particle entered not only increases the wetability of nano fibrous membrane, so that nano fibrous membrane presentation is super hydrophilic-underwater
Superoleophobic state, on the other hand the introducing of negatively charged β-FeOOH further improves the specific surface area of nano fibrous membrane,
Nano fibrous membrane is greatly improved in sewage treatment to the adsorption capacity of dyestuff and heavy metal ion in sewage, while β-
The introducing of FeOOH so that film has the property of photocatalytic degradation, make nano fibrous membrane have under the action of visible light automatically cleaning,
The performance of selfreparing, so that polyacrylonitrile nanofiber film can more efficient circulations use.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is polyacrylonitrile nano obtained in the preparation step of polyacrylonitrile nanofiber film in the embodiment of the present invention 1
The SEM of tunica fibrosa schemes；
Fig. 2 is stabilized polyacrylonitrile nanofiber film progress obtained after stabilization processes in the embodiment of the present invention 1
SEM figure；
Fig. 3 is the SEM figure of the composite nano-fiber membrane for the β-FeOOH/ polyacrylonitrile that the embodiment of the present invention 1 obtains；
Fig. 4 is water process figure of the present invention without the polyacrylonitrile nanofiber film Jing Guo any processing；
Fig. 5 is the water of stabilized polyacrylonitrile nanofiber film obtained after stabilization processes in the embodiment of the present invention 1
Processing figure；
Fig. 6 is made from the polyacrylonitrile nanofiber film (PAN) of the invention without Jing Guo any processing and embodiment 1
Dissolution situation map of the β-FeOOH/ polyacrylonitrile nanofiber film (SPF) in dimethyl acetamide (DMAC) solution；
Fig. 7 is made from the polyacrylonitrile nanofiber film (PAN) of the invention without Jing Guo any processing and embodiment 1
Dissolution situation map of the β-FeOOH/ polyacrylonitrile nanofiber film (SPF) in dimethylformamide (DFM) solution；
Fig. 8 is made from the polyacrylonitrile nanofiber film (PAN) of the invention without Jing Guo any processing and embodiment 1
Dissolution situation map of the β-FeOOH/ polyacrylonitrile nanofiber film (SPF) in dimethyl sulfoxide (DMSO) solution；
Fig. 9 is made from the polyacrylonitrile nanofiber film (PAN) of the invention without Jing Guo any processing and embodiment 1
Dissolution situation map of the β-FeOOH/ polyacrylonitrile nanofiber film (SPF) in N-Methyl pyrrolidone (NMP) solution；
Figure 10 is β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 respectively in dimethyl
Acetamide (DMAC) solution, dimethylformamide (DFM) solution, dimethyl sulfoxide (DMSO) solution, N-Methyl pyrrolidone
(NMP) the dissolution situation map carried out after being impregnated 5 days in solution, sodium chloride solution, sodium hydroxide solution and hydrochloric acid solution；
Figure 11 is β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 respectively in dimethyl
Acetamide (DMAC) solution, dimethylformamide (DFM) solution, dimethyl sulfoxide (DMSO) solution, N-Methyl pyrrolidone
(NMP) test of the contact angle of underwater oil after being impregnated 5 days in solution, sodium chloride solution, sodium hydroxide solution and hydrochloric acid solution
Result figure；
Figure 12 is β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 in dimethylacetamide
Comparison diagram before and after SEM after the immersion of amine (DMAC) solution 5 days；
Figure 13 is that the present invention is contacted in air without the polyacrylonitrile nanofiber film (PAN) Jing Guo any processing
The test result figure at angle；
Figure 14 be β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 in air into
The test result figure of row contact angle；
Figure 15 is that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 carries out just under water
The contact angle test result figure of oily ether, n-hexane, toluene and diesel oil；
Figure 16 is that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 carries out oil-water separation
Emulsion separation result figure；
Figure 17 is that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 carries out grease/dyestuff
Separation front and back UV-visible spectrum；
Figure 18 is β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 in external drive pressure
Handled under power 0.2bar the just oily ether of such as positive oily ether of various water-oil emulsions, n-hexane, toluene, diesel oil, SDS/, SDS/ n-hexane,
Permeation flux result figure is carried out in SDS/ toluene and SDS/ diesel oil；
Figure 19 is that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 is handling various oil
Aqueous emulsion is such as positive oily ether, n-hexane, toluene, diesel oil, the just oily ether of SDS/, SDS/ n-hexane, SDS/ toluene and SDS/ diesel oil
Separative efficiency test result figure；
Figure 20 is that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from the embodiment of the present invention 1 is handling various oil
The cycle-index test chart of such as positive oily ether of aqueous emulsion.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of composite nano-fiber membrane and preparation method thereof of β-FeOOH/ polyacrylonitrile of the embodiment of the present invention
It is specifically described with application.
A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile provided in an embodiment of the present invention, packet
Include following steps:
The preparation of polyacrylonitrile nanofiber film: polyacrylonitrile powder is uniformly mixed with N,N-dimethylformamide solution
Spinning solution is made, polyacrylonitrile nanofiber film, polyacrylonitrile powder and N, N- bis- are then spun by electrostatic spinning apparatus
The ratio of methylformamide solution is 1-1.4g:10mL.
Wherein, when the temperature is low, be easy to cause solution to be lower by mobility, lead to the blocking of spinning nozzle, when temperature compared with
Gao Shi is easy to cause the too fast volatilization of n,N-Dimethylformamide in solution, influences the formation of polyacrylonitrile nanofiber film；
When voltage is lower, electric field force is too small, and electrostatic field force cannot overcome the surface tension of solution, can not form jet stream, can not prepare
Nanofiber can make electrostatic spinning is unstable to be unfavorable for obtaining that surface is smooth, fiber of uniform diameter when voltage is excessive；When connecing
When the distance between receiving apparatus and spinning nozzle are too small, cause the electric field force between spinning nozzle and collection device excessive, be easy to cause
Fibre diameter is inhomogenous, and when apart from excessive, the splitting ability of drop is poor, is unfavorable for forming nanofiber；It therefore, is terrible
The preferable polyacrylonitrile nanofiber film of, uniform diameter smooth to surface, configuration of surface, the item of electrostatic spinning of the embodiment of the present invention
Part are as follows: spinning temperature is 30-38 DEG C, spinning voltage 20-25kv, and receiving distance is 18-22cm, ambient humidity 45-55%, stream
Speed is 0.6-1.2mL/h.Preferably, the condition of electrostatic spinning are as follows: spinning temperature be 35 DEG C, spinning voltage 25kv, receive away from
From for 20cm, ambient humidity 50%, flow velocity 1mL/h.
It should be noted that spinning syringe needle model 22 used in the embodiment of the present invention, but not limited to this, it can also adopt
With the spinning syringe needle of other models, such as No. 18, No. 20 etc..
Wherein, the ratio of polyacrylonitrile powder and n,N-Dimethylformamide solution cannot be too high, the concentration of polyacrylonitrile
It is too high that spinning nozzle is easy to cause to block, can not be too low, not at polyacrylonitrile nanofiber film, the embodiment of the present invention is poly- for too low spinning
The ratio of acrylonitrile powder and N,N-dimethylformamide solution is 1-1.4g:10mL.
Further, the polyacrylonitrile nanofiber film being spun into is dried under conditions of vacuum, is dried under conditions of vacuum
Dry purpose is while not influence polyacrylonitrile nanofiber film again to remove solvent remaining on polyacrylonitrile nanofiber film
Structure.
Further, the condition of drying are as follows: 55-65 DEG C of drying temperature, drying time 10-14h, in this drying condition
Under, solvent remaining on polyacrylonitrile nanofiber film can be made sufficiently to be volatilized.
It should be noted that the molecular weight of polyacrylonitrile powder is 150000, N, N- dimethyl methyl in the embodiment of the present invention
The purity of amide is 99.9%.
Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is protected under conditions of 235-240 DEG C
Warm 0.5-2h keeps the temperature 0.5-2h under conditions of 245-250 DEG C, keeps the temperature 0.5-2h under conditions of 258-262 DEG C, then takes out
It is cooled to room temperature and stabilized polyacrylonitrile nanofiber film is made.
0.5-2h is kept the temperature under conditions of 235-240 DEG C, the polyacrylonitrile in polyacrylonitrile nanofiber film is cyclized
Reaction, keeps the temperature 0.5-2h under conditions of 245-250 DEG C, and polyacrylonitrile occurs oxidation reaction, protects under conditions of 258-262 DEG C
Warm 0.5-2h, polyacrylonitrile occur dehydrogenation reaction, pass through cyclization, oxidation reaction and dehydrogenation reaction, polyacrylonitrile molecule knot
Allosteric transformation improves the stability of polyacrylonitrile nanofiber film, on the one hand makes polyacrylonitrile nano at trapezium structure molecule
Tunica fibrosa has the characteristic of " not melting non-ignitable ", makes polyacrylonitrile nanofiber film in common highly polar organic solvent (N, N- bis-
Methylformamide, dimethyl sulfoxide, acetone etc.) in can be stabilized, answer it in acid, alkali, salt and the harsh of organic reagent
Miscellaneous Sewage Environment can be stabilized, and then can effectively be handled sewage；On the other hand, by above-mentioned reaction,
Oxygen-containing, nitrogen functional group is introduced, can be improved the hydrophilicity of polyacrylonitrile nanofiber film；Simultaneously because polyacrylonitrile fibre
Part high temperature melting, crosslinking, linear molecule are changed into trapezium structure molecule, so that film strips have self-supporting property, this is relative to biography
The polyacrylonitrile nanofiber film of system improves the operability matter of film, is conducive to industrialized large-scale production.
Biomineralization processing: by the proportional arrangement of liquor ferri trichloridi and hydrochloric acid solution 2:1 by volume at mixed solution,
Stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 1-3min, it is then anti-under conditions of 55-65 DEG C
10-14h is answered, the composite nano-fiber membrane (SPN) of obtained β-FeOOH/ polyacrylonitrile is then cleaned, dried.
First by liquor ferri trichloridi and mixed in hydrochloric acid it is uniform after, by stabilized polyacrylonitrile nanofiber be placed in mixing it is molten
It is stirred in liquid, reacts 10-14h under conditions of the solution after stirring is then placed in 55-65 DEG C, in order at 55-65 DEG C
Under conditions of, ferric trichloride reacts in acid condition generates β-FeOOH, and reaction equation is as follows:
Fe3++3H2O→Fe(OH)3+3H+
Fe(OH)3→β-FeOOH+H2O
It is handled by biomineralization, in the process, the β-FeOOH nano particle of introducing not only increases the wetting of film
Property, so that super hydrophilic-underwater superoleophobic state is presented in film, when carrying out sewage treatment, hydrophilicity can be improved the saturating of water
Rate is crossed, underwater superoleophobic performance can be carried out effectively water-oil separation etc.；On the other hand the introducing of negatively charged β-FeOOH,
The specific surface area of film can be further improved, improves film to the adsorption capacity of dyestuff, heavy metal in sewage；β-simultaneously
FeOOH is introduced into the surface of film as a kind of particular semiconductor material, so that film is had the performance of photocatalytic degradation, can
Under light-exposed, nano fibrous membrane can be by the contaminant degradation of film surface, the problem of reaching repair membrane, improves making profits again for film
With ability, film efficient circulation is used.
Wherein, liquor ferri trichloridi is to be dissolved in ferric trichloride in deionized water being made, ferric trichloride and deionized water
Ratio is 16-20mg:1mL, and in the embodiment of the present invention, the concentration of hydrochloric acid is 10mmol/L in hydrochloric acid solution.
Further, the condition dried in biomineralization processing are as follows: drying temperature is 55-65 DEG C, drying time 0.2-
0.4h, in order to dry the moisture of cleaning.
The present invention provides a kind of preparation methods of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, and method is simple,
At low cost, the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile obtained has excellent stability energy and absorption property.
The composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile provided by the invention, is made by the above method, have compared with
Stability well, mechanical performance, while there is super hydrophilic-underwater superoleophobic property, adsorption efficiency is high, benefit can be recycled
In industrialization large-scale production.
A kind of application of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile provided by the invention in sewage treatment, place
It is good to manage effect, can be repeated several times use.It may be acid, alkali, in the harsh complicated Sewage Environment of salt and organic reagent, on
The composite nano-fiber membrane for stating β-FeOOH/ polyacrylonitrile can be stabilized, and be able to carry out water-oil separating, dyestuff and heavy metal
Removal.
Embodiment 1
A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, comprising the following steps:
The preparation of polyacrylonitrile nanofiber film: by 1.2 polyacrylonitrile powders and 10mL N,N-dimethylformamide solution
It is uniformly mixed and spinning solution is made, polyacrylonitrile nanofiber film is then spun by electrostatic spinning apparatus, then in vacuum
Under the conditions of dry, wherein the condition of spinning are as follows: spinning temperature be 35 DEG C, spinning voltage 25kv, receive distance be 20cm, ring
Border humidity 50%, flow velocity 1mL/h, the condition of drying are as follows: 60 DEG C of drying temperature, drying time 12h.
Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is kept the temperature under conditions of 238 DEG C
0.5h keeps the temperature 0.5h under conditions of 248 DEG C, keeps the temperature 0.5h under conditions of 260 DEG C, then takes out to be cooled to room temperature and is made steady
Surely the polyacrylonitrile nanofiber changed；
Biomineralization processing: ferric trichloride being dissolved in, the liquor ferri trichloridi that concentration is 18mg/ml be made in deionized water,
Configuration concentration is the hydrochloric acid solution of 10mmol/L, by liquor ferri trichloridi and hydrochloric acid solution by volume 2:1 proportional arrangement at
Stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 1min, then in 60 DEG C of condition by mixed solution
Lower reaction 12h then takes out nano fibrous membrane and carries out that 3 cleanings, β-is made in drying 0.3h under conditions of 60 DEG C with deionized water
The composite nano-fiber membrane of FeOOH/ polyacrylonitrile.
Embodiment 2
A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, comprising the following steps:
The preparation of polyacrylonitrile nanofiber film: by 1g polyacrylonitrile powder and 10mL N,N-dimethylformamide solution
It is uniformly mixed and spinning solution is made, polyacrylonitrile nanofiber film is then spun by electrostatic spinning apparatus, then in vacuum
Under the conditions of dry, wherein the condition of spinning are as follows: spinning temperature be 30 DEG C, spinning voltage 20kv, receive distance be 18cm, ring
Border humidity 45%, flow velocity 0.6mL/h, the condition of drying are as follows: 55 DEG C of drying temperature, drying time 10h.
Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is kept the temperature under conditions of 235 DEG C
2h keeps the temperature 2h under conditions of 245 DEG C, keeps the temperature 2h under conditions of 258 DEG C, then takes out to be cooled to room temperature and is made stabilized
Polyacrylonitrile nanofiber；
Biomineralization processing: ferric trichloride being dissolved in, the liquor ferri trichloridi that concentration is 16mg/ml be made in deionized water,
Configuration concentration is the hydrochloric acid solution of 10mmol/L, by liquor ferri trichloridi and hydrochloric acid solution by volume 2:1 proportional arrangement at
Stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 3min, then in 55 DEG C of condition by mixed solution
Lower reaction 10h then takes out nano fibrous membrane and carries out that 3 cleanings, β-is made in drying 0.2h under conditions of 55 DEG C with deionized water
The composite nano-fiber membrane of FeOOH/ polyacrylonitrile.
Embodiment 3
A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, comprising the following steps:
The preparation of polyacrylonitrile nanofiber film: 1.4g polyacrylonitrile powder and 10mL N,N-dimethylformamide is molten
Liquid is uniformly mixed and spinning solution is made, and then polyacrylonitrile nanofiber film is spun by electrostatic spinning apparatus, then in vacuum
Under conditions of dry, wherein the condition of spinning are as follows: spinning temperature be 38 DEG C, spinning voltage 25kv, receive distance be 22cm,
Ambient humidity 55%, flow velocity 1.2mL/h, the condition of drying are as follows: 65 DEG C of drying temperature, drying time 14h.
Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is kept the temperature under conditions of 240 DEG C
0.8h keeps the temperature 0.8h under conditions of 250 DEG C, keeps the temperature 0.8h under conditions of 262 DEG C, then takes out to be cooled to room temperature and is made steady
Surely the polyacrylonitrile nanofiber changed；
Biomineralization processing: ferric trichloride being dissolved in, the liquor ferri trichloridi that concentration is 20mg/ml be made in deionized water,
Configuration concentration is the hydrochloric acid solution of 10mmol/L, by liquor ferri trichloridi and hydrochloric acid solution by volume 2:1 proportional arrangement at
Stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 3min, then in 65 DEG C of condition by mixed solution
Lower reaction 14h then takes out nano fibrous membrane and carries out that 3 cleanings, β-is made in drying 0.4h under conditions of 65 DEG C with deionized water
The composite nano-fiber membrane of FeOOH/ polyacrylonitrile.
Embodiment 4
A kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, comprising the following steps:
The preparation of polyacrylonitrile nanofiber film: 1.1g polyacrylonitrile powder and 10mL N,N-dimethylformamide is molten
Liquid is uniformly mixed and spinning solution is made, and then polyacrylonitrile nanofiber film is spun by electrostatic spinning apparatus, then in vacuum
Under conditions of dry, wherein the condition of spinning are as follows: spinning temperature be 32 DEG C, spinning voltage 22kv, receive distance be 21cm,
Ambient humidity 52%, flow velocity 0.8mL/h, the condition of drying are as follows: 61 DEG C of drying temperature, drying time 11h.
Stabilization processes: polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is kept the temperature under conditions of 236 DEG C
1.2h keeps the temperature 1.2h under conditions of 246 DEG C, keeps the temperature 1.2h under conditions of 261 DEG C, then takes out to be cooled to room temperature and is made steady
Surely the polyacrylonitrile nanofiber changed；
Biomineralization processing: ferric trichloride being dissolved in, the liquor ferri trichloridi that concentration is 19mg/ml be made in deionized water,
Configuration concentration is the hydrochloric acid solution of 10mmol/L, by liquor ferri trichloridi and hydrochloric acid solution by volume 2:1 proportional arrangement at
Stabilized polyacrylonitrile nanofiber film is placed in mixed solution and stirs 3min, then in 60 DEG C of condition by mixed solution
Lower reaction 14h then takes out nano fibrous membrane and carries out that 3 cleanings, β-is made in drying 0.4h under conditions of 60 DEG C with deionized water
The composite nano-fiber membrane of FeOOH/ polyacrylonitrile.
Experimental example
1, polyacrylonitrile nanofiber film obtained in the preparation step of 1 polyacrylonitrile nanofiber film of embodiment is carried out
The characterization (shown in Fig. 1) of scanning electron microscope (SEM), stabilized polyacrylonitrile nanofiber film obtained carries out after stabilization processes
The characterization (shown in Fig. 2) of SEM, the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile obtained carries out after biomineralization processing
The characterization (shown in Fig. 3) of SEM, as can be seen from Figure 1 polyacrylonitrile nanofiber film uniform diameter obtained, fibre morphology
It is good；As can be seen from Figure 2 polyacrylonitrile nanofiber film tangles, even closer between nanofiber, illustrates to stabilize
Its mechanical performance of treated fiber has a certain upgrade；From figure 3, it can be seen that polyacrylonitrile nano is fine after biomineralization processing
Dimension introduces many β-FeOOH mineral grains.
2, by not by any processing polyacrylonitrile nanofiber film and embodiment 1 made after stabilization processes
The stabilized polyacrylonitrile nanofiber film obtained clamps the effect contrast figure after aqueous solution with clip respectively, from Fig. 4
It can be seen that without cuddling up in a heap after aqueous solution lifts by the polyacrylonitrile nanofiber of any processing, it can from Fig. 5
To find out that the stabilized polyacrylonitrile nanofiber film obtained after stabilization processes of embodiment 1 lifts by aqueous solution
Afterwards, polyacrylonitrile nanofiber film is not cuddled up in a heap, and also has preferable spreading, is illustrated by polyacrylonitrile of the invention
Nano fibrous membrane improves water-swellable and the support of polyacrylonitrile after stabilization processes, this is for polyacrylonitrile nano fibre
The subsequent processing of dimension film is very important.
3, by not by any processing polyacrylonitrile nanofiber film (PAN) and embodiment 1 made from β-
FeOOH/ polyacrylonitrile nanofiber film (SPF) is respectively in dimethyl acetamide (DMAC) solution, dimethylformamide (DFM)
Dissolution phenomena in solution, dimethyl sulfoxide (DMSO) solution and N-Methyl pyrrolidone (NMP) solution, as a result such as Fig. 6-Fig. 9
Shown, the polyacrylonitrile nanofiber film (PAN) not Jing Guo any processing is in dimethyl acetamide (DMAC) solution, dimethyl
In different time in formamide (DFM) solution, dimethyl sulfoxide (DMSO) solution and N-Methyl pyrrolidone (NMP) solution
It is dissolved after (1-8s), and β-FeOOH/ polyacrylonitrile nanofiber film (SPF) is in dimethyl acetamide made from embodiment 1
(DMAC) solution, dimethylformamide (DFM) solution, dimethyl sulfoxide (DMSO) solution and N-Methyl pyrrolidone (NMP)
It is not all dissolved after impregnating 10s in solution, illustrates β-FeOOH/ polyacrylonitrile nanofiber film made from the embodiment of the present invention
(SPF) organic solvent is had excellent stability, this is one for the sewage (containing organic solvent) for handling various complexity
A very important property.
4, by β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 respectively in dimethyl acetamide
(DMAC) solution, dimethylformamide (DFM) solution, dimethyl sulfoxide (DMSO) solution and N-Methyl pyrrolidone (NMP)
It carries out observing its dissolution phenomena after impregnating 5 days in solution, sodium chloride solution, sodium hydroxide solution and hydrochloric acid solution, as a result such as
Shown in Figure 10, and the test of the contact angle of underwater oil is carried out, as a result as shown in figure 11, and β-FeOOH/ polyacrylonitrile nano is fine
β-FeOOH/ polyacrylonitrile nanofiber film after tieing up film (SPF) and being impregnated 5 days in dimethyl acetamide (DMAC) solution
(SPF) SEM test is carried out, as a result as shown in figure 12.
It can be seen from fig. 10 that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) is respectively in dimethyl acetamide
(DMAC) solution, dimethylformamide (DFM) solution, dimethyl sulfoxide (DMSO) solution and N-Methyl pyrrolidone (NMP)
It is not dissolved after being impregnated 5 days in solution, sodium chloride solution, sodium hydroxide solution and hydrochloric acid solution, there is preferable stability
Energy.
It can be seen from fig. 11 that before and after contact angle, there is no significant changes, illustrate β-FeOOH/ polyacrylonitrile again
The stability of nano fibrous membrane (SPF) is preferable.
In figure 12 it can be seen that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) and in dimethyl acetamide
(DMAC) SEM of the β-FeOOH/ polyacrylonitrile nanofiber film (SPF) after impregnating 5 days in solution schemes no significant change, into
One step illustrates its better stability.
5, by not by any processing polyacrylonitrile nanofiber film (PAN) and embodiment 1 made from β-
FeOOH/ polyacrylonitrile nanofiber film (SPF) carries out the test of contact angle in air respectively, as a result as illustrated in figs. 13-14.
It can be seen from the figure that the aerial water contact angle 10s of polyacrylonitrile nanofiber film (PAN) not Jing Guo any processing
Variation is 118 ° or so less afterwards, and contact angle is reduced to 0 from 15.8 ° after β-FeOOH/ polyacrylonitrile nanofiber film (SPF) 10s,
Illustrate that β-FeOOH/ polyacrylonitrile nanofiber film (SPF) prepared by the present invention has preferable hydrophilicity.
6, β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 is carried out to positive oily ether, just oneself under water
The contact angle test of alkane, toluene and diesel oil, as a result as shown in figure 15, it can be seen that β-FeOOH/ polyacrylonitrile nanofiber film
(SPF) there is underwater superoleophobic property.
7, β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 is subjected to oil-water separation emulsion point
From as a result as shown in figure 16, the left side is after separating, and the right is before separating, it can be seen that the solution after separation is more clarified,
Illustrate that separating effect is preferable.
8, β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 carries out purple before and after grease/dye separation
Outside-visible light spectrogram, as a result as described in Figure 17, as can be seen from the figure its separating effect is preferable.
10, by β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 in external driving pressure 0.2bar
The calculating of permeation flux is carried out in such as positive oily ether of the lower various water-oil emulsions of processing, n-hexane, toluene and diesel oil and added with table
It is carried out in the just oily ether of the stable oil-in-water emulsion such as SDS/ of face activating agent, SDS/ n-hexane, SDS/ toluene and SDS/ diesel oil
The calculating of permeation flux, as a result as shown in figure 18, it can be seen from the figure that its permeation flux is preferable.
11, β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 is handling various water-oil emulsions such as
The separative efficiency survey of positive oil ether, n-hexane, toluene, diesel oil, SDS/ just oily ether, SDS/ n-hexane, SDS/ toluene and SDS/ diesel oil
Examination, as a result as shown in figure 19, TOC are total phosphorus content in filtrate, because various oil are all organic matter, using filtrate TOC
The residual volume for indicating oil-containing in water can find out, separative efficiency is higher from figure, up to 98% or more.
12, β-FeOOH/ polyacrylonitrile nanofiber film (SPF) made from embodiment 1 is handling various water-oil emulsions such as
The cycle-index of positive oil ether, as a result as shown in figure 20, permeation flux and filtrate TOC content be not significantly every time under multiple circulation
On the one hand decaying and rising represent film with certain stability and preferable resistance to oily stain energy.
In conclusion a kind of composite nano-fiber membrane and preparation method thereof of β-FeOOH/ polyacrylonitrile provided by the invention
With application, there is preferable stability, mechanical performance, while there is super hydrophilic-underwater superoleophobic property, adsorption efficiency
Height can be recycled conducive to industrialization large-scale production.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, it is characterised in that: the following steps are included:
The preparation of polyacrylonitrile nanofiber film: polyacrylonitrile powder is uniformly mixed with N,N-dimethylformamide solution and is made
Then spinning solution is spun into polyacrylonitrile nanofiber film, the polyacrylonitrile powder and the N by electrostatic spinning apparatus,
The ratio of dinethylformamide solution is 1-1.4g:10mL；
Stabilization processes: the polyacrylonitrile nanofiber film is subjected to gradient increased temperature processing, is protected under conditions of 235-240 DEG C
Warm 0.5-2h keeps the temperature 0.5-2h under conditions of 245-250 DEG C, keeps the temperature 0.5-2h under conditions of 258-262 DEG C, then takes out
It is cooled to room temperature and stabilized polyacrylonitrile nanofiber film is made；
Biomineralization processing:, will be steady by the proportional arrangement of liquor ferri trichloridi and hydrochloric acid solution 2:1 by volume at mixed solution
Surely the polyacrylonitrile nanofiber film changed, which is placed in the mixed solution, stirs 1-3min, then anti-under conditions of 55-65 DEG C
10-14h is answered, the composite nano-fiber membrane of obtained β-FeOOH/ polyacrylonitrile is then cleaned, dried.
2. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 1, feature exist
In: the condition of electrostatic spinning are as follows: spinning temperature is 30-38 DEG C, spinning voltage 20-25kv, and receiving distance is 18-22cm, ring
Border humidity 45-55%, flow velocity 0.6-1.2mL/h.
3. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 2, feature exist
In: the condition of electrostatic spinning are as follows: spinning temperature is 35 DEG C, spinning voltage 25kv, and receiving distance is 20cm, ambient humidity
50%, flow velocity 1mL/h.
4. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 1, feature exist
In: in the preparation step of the polyacrylonitrile nanofiber film, the item of the polyacrylonitrile nanofiber film that is spun into vacuum
It is dried under part.
5. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 4, feature exist
In: the condition of the drying are as follows: 55-65 DEG C of drying temperature, drying time 10-14h.
6. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 1, feature exist
In: the liquor ferri trichloridi is to be dissolved in ferric trichloride in deionized water being made, the ferric trichloride and the deionized water
Ratio be 16-20mg:1mL.
7. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 1, feature exist
In: the condition dried in the biomineralization processing step are as follows: drying temperature is 55-65 DEG C, drying time 0.2-0.4h.
8. the preparation method of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile according to claim 1, feature exist
In: the concentration of hydrochloric acid is 10mmol/L in the hydrochloric acid solution.
9. a kind of composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile, it is characterised in that: as described in claim any one of 1-8
β-FeOOH/ polyacrylonitrile composite nano-fiber membrane preparation method be made.
10. application of the composite nano-fiber membrane of β-FeOOH/ polyacrylonitrile as claimed in claim 9 in sewage treatment.
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